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1. Reductive cleavage of N , N ′-di- tert -butylcarbodiimide generates tert -butylcyanamide ligands, (Me ₃ CNCN) ⁻ , that bind potassium both end-on and side-on in the same single crystal

   https://doi.org/10.1107/S205698902000732X  

   Chung, Amanda B.; Ziller, Joseph W.; Evans, William J. (July 2020, Acta Crystallographica Section E Crystallographic Communications)

   null (Ed.)

   N , N ′-Di- tert -butylcarbodiimide, Me 3 CN=C=NCMe 3 , undergoes reductive cleavage in the presence of the Gd II complex, [K(18-crown-6) 2 ][Gd II (N R 2 ) 3 ] ( R = SiMe 3 ), to form a new type of ligand, the tert -butylcyanamide anion, (Me 3 CNCN) − . This new ligand can bind metals with one or two donor atoms as demonstrated by the isolation of a single crystal containing potassium salts of both end-on and side-on bound tert -butylcyanamide anions, (Me 3 CNCN) − . The crystal contains [K(18-crown-6)(H 2 O)][NCNCMe 3 - kN ], in which one ( t BuNCN) − anion is coordinated end-on to potassium ligated by 18-crown-6 and water, as well as [K(18-crown-6)][η 2 -NCNCMe 3 ], in which an 18-crown-6 potassium is coordinated side-on to the terminal N—C linkage. This single crystal also contains one equivalent of 1,3-di- tert -butyl urea, (C 9 H 20 N 2 O), which is involved in hydrogen bonding that may stabilize the whole assembly, namely, aqua( tert -butylcyanamidato)(1,4,7,10,13,16-hexaoxacyclooctadecane)potassium(I)–( tert -butylcyanamidato)(1,4,7,10,13,16-hexaoxacyclooctadecane)potassium(I)– N , N ′-di- tert -butylcarbodiimide (1/1/1) [K(C 5 H 9 N 2 )(C 12 H 24 O 6 )]·[K(C 5 H 9 N 2 )(C 12 H 24 O 6 )(H 2 O)]·C 9 H 20 N 2 . 

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2. Synthesis and reactivity of a nickel( ii ) thioperoxide complex: demonstration of sulfide-mediated N ₂ O reduction

   https://doi.org/10.1039/C8SC02536C  

   Hartmann, Nathaniel J.; Wu, Guang; Hayton, Trevor W. (January 2018, Chemical Science)

   The “masked” terminal nickel sulfide [K(18-crown-6)][L^tBuNi^II(S)] mediates the reduction of N₂O by CO,viathe thioperoxide complex [K(18-crown-6)][L^tBuNi^II(η²-SO)]. 

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3. The importance of the counter-cation in reductive rare-earth metal chemistry: 18-crown-6 instead of 2,2,2-cryptand allows isolation of [Y ^II (NR ₂ ) ₃ ] ¹⁻ and ynediolate and enediolate complexes from CO reactions

   https://doi.org/10.1039/C9SC05794C  

   Ryan, Austin J.; Ziller, Joseph W.; Evans, William J. (February 2020, Chemical Science)

   The use of 18-crown-6 (18-c-6) in place of 2.2.2-cryptand (crypt) in rare earth amide reduction reactions involving potassium has proven to be crucial in the synthesis of Ln( ii ) complexes and isolation of their CO reduction products. The faster speed of crystallization with 18-c-6 appears to be important. Previous studies have shown that reduction of the trivalent amide complexes Ln(NR 2 ) 3 (R = SiMe 3 ) with potassium in the presence of 2.2.2-cryptand (crypt) forms the divalent [K(crypt)][Ln II (NR 2 ) 3 ] complexes for Ln = Gd, Tb, Dy, and Tm. However, for Ho and Er, the [Ln(NR 2 ) 3 ] 1− anions were only isolable with [Rb(crypt)] 1+ counter-cations and isolation of the [Y II (NR 2 ) 3 ] 1− anion was not possible under any of these conditions. We now report that by changing the potassium chelator from crypt to 18-crown-6 (18-c-6), the [Ln(NR 2 ) 3 ] 1− anions can be isolated not only for Ln = Gd, Tb, Dy, and Tm, but also for Ho, Er, and Y. Specifically, these anions are isolated as salts of a 1 : 2 potassium : crown sandwich cation, [K(18-c-6) 2 ] 1+ , i.e. [K(18-c-6) 2 ][Ln(NR 2 ) 3 ]. The [K(18-c-6) 2 ] 1+ counter-cation was superior not only in the synthesis, but it also allowed the isolation of crystallographically-characterizable products from reactions of CO with the [Ln(NR 2 ) 3 ] 1− anions that were not obtainable from the [K(crypt)] 1+ analogs. Reaction of CO with [K(18-c-6) 2 ][Ln(NR 2 ) 3 ], generated in situ , yielded crystals of the ynediolate products, {[(R 2 N) 3 Ln] 2 (μ-OCCO)} 2− , which crystallized with counter-cations possessing 2 : 3 potassium : crown ratios, i.e. {[K 2 (18-c-6) 3 ]} 2+ , for Gd, Dy, Ho. In contrast, reaction of CO with a solution of isolated [K(18-c-6) 2 ][Gd(NR 2 ) 3 ], produced crystals of an enediolate complex isolated with a counter-cation with a 2 : 2 potassium : crown ratio namely [K(18-c-6)] 2 2+ in the complex [K(18-c-6)] 2 {[(R 2 N) 2 Gd 2 (μ-OCHCHO) 2 ]}. 

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4. Site‐Specific Reduction‐Induced Hydrogenation of a Helical Bilayer Nanographene with K and Rb Metals: Electron Multiaddition and Selective Rb ⁺ Complexation

   https://doi.org/10.1002/anie.202115747  

   Zhou, Zheng; Fernández‐García, Jesús M.; Zhu, Yikun; Evans, Paul J.; Rodríguez, Rafael; Crassous, Jeanne; Wei, Zheng; Fernández, Israel; Petrukhina, Marina A.; Martín, Nazario (December 2021, Angewandte Chemie International Edition)

   Abstract The chemical reduction of π‐conjugated bilayer nanographene1(C₁₃₈H₁₂₀) with K and Rb in the presence of 18‐crown‐6 affords [K⁺(18‐crown‐6)(THF)₂][{K⁺(18‐crown‐6)}₂(THF)_0.5][C₁₃₈H₁₂₂³⁻] (2) and [Rb⁺(18‐crown‐6)₂][{Rb⁺(18‐crown‐6)}₂(C₁₃₈H₁₂₂³⁻)] (3). Whereas K⁺cations are fully solvent‐separated from the trianionic core thus affording a “naked”1^.3−anion, Rb⁺cations are coordinated to the negatively charged layers of1^.3−. According to DFT calculations, the localization of the first two electrons in the helicene moiety leads to an unprecedented site‐specific hydrogenation process at the carbon atoms located on the edge of the helicene backbone. This uncommon reduction‐induced site‐specific hydrogenation provokes dramatic changes in the (electronic) structure of1as the helicene backbone becomes more compressed and twisted upon chemical reduction, which results in a clear slippage of the bilayers. 

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5. Crystal structure of (1,4,7,10,13,16-hexaoxacyclooctadecane-κ ⁶ O )potassium-μ-oxalato-triphenylstannate(IV), the first reported 18-crown-6-stabilized potassium salt of triphenyloxalatostannate

   https://doi.org/10.1107/S2056989024007758  

   Song, Xueqing; Li, William; Torres, Yolanda; Greaves, Tazena (September 2024, Acta Crystallographica Section E Crystallographic Communications)

   The title complex, (1,4,7,10,13,16-hexaoxacyclooctadecane-1κ⁶O)(μ-oxalato-1κ²O¹,O²:2κ²O^1′,O^2′)triphenyl-2κ³C-potassium(I)tin(IV), [KSn(C₆H₅)₃(C₂O₄)(C₁₂H₂₄O₆)] or K[18-Crown-6][(C₆H₅)₃SnO₄C₂], was synthesized. The complex consists of a potassium cation coordinated to the six oxygen atoms of a crown ether molecule and the two oxygen atoms of the oxalatotriphenylstannate anion. It crystallizes in the monoclinic crystal system within the space groupP2₁. The tin atom is coordinated by one chelating oxalate ligand and three phenyl groups, forming acis-trigonal–bipyramidal geometry around the tin atom. The cations and anions form ion pairs, linked through carbonyl coordination to the potassium atoms. The crystal structure features C—H...O hydrogen bonds between the oxygen atoms of the oxalate group and the hydrogen atoms of the phenyl groups, resulting in an infinite chain structure extending alonga-axis direction. The primary inter-chain interactions are van der Waals forces. 

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